TW202116861A - Electrical connector formed from a polymer composition having a low dielectric constant and dissipation factor - Google Patents

Abstract

An electrical connector is disclosed that comprises at least two opposing walls between which a passageway is defined for receiving a contact pin, wherein the walls have a width of about 500 micrometers or less and are formed from a polymer composition that comprises a polymer matrix containing at least one polymer having a glass transition temperature of about 30℃ or more in an amount of 30 wt% or more of the composition. The polymer composition exhibits a dielectric constant of about 4 or less and a dissipation factor of about 0.02 or less, as determined at a frequency of 10 GHz.

Description

Electrical connector formed by polymer composition with low dielectric constant and dissipation factor

High-frequency radio signal communication has become more and more popular. For example, the demand for data transmission speed to increase the connectivity of wireless smart phones has driven the demand for high-frequency components, including those components that are configured to operate at 5G spectrum frequencies. Components used to electrically connect 5G components, such as antennas, front-end modules, and the like, generally require small-scale features. The trend towards miniaturization has further increased the objective need for smaller, high-frequency 5G connectors. A variety of materials can be used for 5G connectors. However, the characteristics of such materials may limit miniaturization and/or improperly permit interference with electrical connections via 5G connectors. In particular, such materials can exhibit relatively high dielectric constants and dissipation factors, which may make such materials difficult to use in certain applications. Even in addition, such materials may not exhibit the required balance between dielectric properties, thermal properties, and mechanical properties.

Therefore, there is a need for an electrical connector formed by a polymer composition that can have a relatively low dielectric constant and a relatively low dissipation factor, but still maintain excellent mechanical properties and processability (for example, low viscosity).

According to an embodiment of the present invention, an electrical connector is disclosed, which includes at least two opposite walls defining a passageway for accommodating connection pins therebetween, wherein the walls have a width of about 500 microns or less and are composed of The polymer composition of the matrix is formed, and the polymer matrix contains at least one polymer having a glass transition temperature of about 30° C. or more and an amount of about 30 wt% or more of the composition. The polymer composition exhibits a dielectric constant of about 4 or less and a dissipation factor of about 0.02 or less, as measured at a frequency of 10 GHz.

According to another embodiment of the present invention, a 5G radio frequency communication system is disclosed, which includes a radio frequency component configured to operate at greater than about 3 GHz, the radio frequency component including connection pins. The radio frequency component may include a connection pin and an electrical connector coupled to the radio frequency component, wherein the electrical connector includes at least two opposite walls defining an aisle therebetween, and the connection pin of the radio frequency component is accommodated in the aisle of the electrical connector, Wherein the walls have a width of about 500 microns or less, and the walls are formed of a polymer composition as defined above.

The other features and aspects of the present invention are described in more detail below.

Cross reference of related applications

This application claims that the filing date is US Provisional Patent Application No. 62/898,202 on September 10, 2019; the filing date is US Provisional Patent Application No. 62/994,317 on March 25, 2020; the filing date is 2020 U.S. Provisional Patent Application No. 63/008,983 on April 13, 2020; U.S. Provisional Application No. 63/038,965 on June 15, 2020 and U.S. Provisional Application on July 27, 2020 For the benefit of document No. 63/056,848, these provisional applications are incorporated herein by reference in their entirety.

Those who are generally familiar with the art should understand that this discussion is only a description of exemplary embodiments, and is not intended to limit the broader aspects of the present invention.

Generally speaking, the present invention relates to a thin-walled electrical connector that can be used in 5G applications. Specifically, the thin-walled electrical connector may be formed of a polymer composition containing a polymer matrix including at least one polymer having a glass transition temperature of about 40°C or greater. The polymer composition can be used for such applications due to its relatively low dielectric constant (D _k ) and dissipation factor (D _f ), as well as its good mechanical properties and good processability.

The electrical connector can have various configurations within the scope of the present invention. As an example, the electrical connector may define a plurality of aisles or spaces between opposing walls. The aisle can accommodate connection pins to facilitate a large number of independent electrical connections by the pins.

The electrical connector can also be extremely compact due to the polymer composition from which it is formed. For example, the polymer composition can exhibit excellent flow characteristics for forming the minimal features required to form electrical connectors as described herein, while also exhibiting minimal bending when exposed to heat. In this regard, the walls may have relatively thin respective widths "w", such as about 500 microns or less, in some embodiments about 400 microns or less, in some embodiments about 25 microns to about 350 microns, And in some embodiments, it is about 50 microns to about 300 microns.

According to an aspect of the present invention, a particularly suitable electrical connector 100 is shown in FIG. 1A. FIG. 1B depicts an enlarged view of the electrical connector 100 of FIG. 1A. As shown, insertion aisles or spaces 225 are defined between opposing walls 224, which can accommodate connection pins to facilitate a large number of independent electrical connections. The electrical connector 100 can be extremely compact. More specifically, the wall 224 may have a relatively thin, such as a respective width "w" within the range described above.

Another embodiment of the electrical connector 200 is depicted in FIG. 2. The board-side part C2 can be mounted on the surface of the circuit board P. The connector 200 may also include a wiring material side portion C1 that is configured to connect the discrete wires 3 to the circuit board P by being coupled to the board side connector C2. The board side portion C2 may include a first housing 10 having a fitting recess 10a into which the wiring material side connector C1 is fitted and a configuration that is thin and long in the lateral direction of the housing 10. The wiring material side portion C1 may also include a second housing 20 which is thin and long in the lateral direction of the housing 20. In the second housing 20, a plurality of terminal accommodating cavities 22 may be provided in parallel along the transverse direction, so as to produce a two-layer array including upper and lower terminal accommodating cavities 22. The terminal 5 installed to the distal end of the discrete wire 3 can be accommodated in each of the terminal accommodating cavities 22. If necessary, locking parts 28 (joining parts) can also be provided on the housing 20, and the locking parts 28 correspond to the connecting parts (not shown in the figure) on the board-side connector C2.

As discussed above, the inner wall of the first housing 10 and/or the second housing 20 may be relatively thin (for example, may have a relatively small width dimension), and may be formed of the polymer composition of the present invention.

The electrical connector can be formed of a polymer composition with a relatively low dielectric constant and dissipation factor. By providing polymer compositions with such dielectric properties, this can help minimize signal loss and improve performance when used in specific applications, such as signal transmission applications and specifically related to 5G communications. . As used in this article, "5G" usually refers to high-speed data communication within radio frequency signals. 5G networks and systems can transmit data at significantly faster rates than previous generation data communication standards (for example, "4G", "LTE"). Different standards and specifications for quantitative 5G communication requirements have been issued. As an example, in 2015, the International Telecommunications Union (ITU) released the International Mobile Telecommunications-2020 ("IMT-2020") standard. The IMT-2020 standard specifies different data transmission criteria for 5G (for example, downlink and uplink data rates, delays, etc.). The IMT-2020 standard limits the uplink and downlink peak data rate to the minimum data rate that the 5G system must support for uploading and downloading data. The IMT-2020 standard sets the downlink peak data rate requirement to 20 Gbit/s and the uplink peak data rate to 10 Gbit/s.

As another example, Third Generation Partnership Project ^{(3 rd Generation Partnership Project; 3GPP} ) recently issued new 5G standards, referred to as "5G NR." In 2018, 3GPP issued "Release 15" to limit the "Phase 1" used for 5G NR standardization. 3GPP generally defines 5G frequency bands as "Frequency Range 1" (FR1) (including sub-6GHz frequencies) and "Frequency Range 2" (FR2), with frequency bands ranging from 20 to 60 GHz. However, as used in this article, "5G frequency" can refer to systems that utilize frequencies greater than 60 GHz, for example, varying up to 80 GHz, up to 150 GHz, and up to 300 GHz. As used herein, "5G frequency" may refer to about 2.5 GHz or higher, in some embodiments about 3.0 GHz or higher, in some embodiments about 3 GHz to about 300 GHz or higher, and in some embodiments In an example, about 4 GHz to about 80 GHz, in some embodiments about 5 GHz to about 80 GHz, in some embodiments about 20 GHz to about 80 GHz, and in some embodiments about 28 GHz to about 60 GHz frequency.

Under the standards issued by 3GPP (such as Release 15 (2018)) and/or IMT-2020 standards, the connectors described in this article can be used in radio frequency systems that can meet "5G" or obtain "5G" qualifications. To achieve such high-speed data communication at high frequencies, antenna elements and arrays generally use small feature sizes/spacing (for example, fine pitch technology) and/or advanced materials that can improve antenna performance. For example, the characteristic size (the spacing between antenna elements, the width of the antenna element), etc. generally depend on the wavelength ("λ") of the required transmitting and/or receiving radio frequency that propagates through the substrate dielectric on which the antenna element is formed ) Depends on (for example, nλ/4, where n is an integer). In addition, beamforming and/or beam steering can be used to facilitate reception and transmission in multiple frequency ranges or channels (e.g., MIMO, massive MIMO).

Electrical connectors can also reduce or prevent interference (eg, "cross interference") between signals emitted on adjacent or nearby pins due to the dielectric properties of the polymer composition that forms them. For example, the dielectric constant of the polymer composition may be about 4 or less, in some embodiments about 3.7 or less, in some embodiments about 3.5 or less, in some embodiments about 0.5 to About 3.4, and in some embodiments, about 1.0 to about 3.2, as measured by the post-splitting resonator method at a frequency of 10 GHz. In addition, the dissipation factor (a measure of energy loss rate) of the polymer composition may be about 0.02 or less, in some embodiments about 0.015 or less, in some embodiments about 0.01 or less, in some embodiments It is about 0.001 to about 0.01 in embodiments, and about 0.001 to about 0.006 in some embodiments, as measured by the post-splitting resonator method at a frequency of 10 GHz.

In some embodiments, the polymer composition may employ at least one additive that allows the dielectric constant of the polymer matrix to be reduced. For example, the use of such additives (for example, hollow inorganic fillers) can reduce the dielectric constant of the polymer matrix by about 2% or more, in some embodiments about 3% or more, in some embodiments From about 3.5% to about 50%, and in some embodiments from about 4% to about 30%. Similarly, the polymer composition may employ at least one additive that allows the dissipation factor of the polymer matrix to be reduced. For example, the use of such additives (for example, hollow inorganic fillers) can reduce the dissipation factor of the polymer matrix by about 2% or more, in some embodiments about 3% or more, in some embodiments From about 3.5% to about 50%, and in some embodiments from about 4% to about 30%.

Conventionally, it is also believed that a polymer composition exhibiting this combination of low dielectric constant and low dissipation factor will not have sufficiently good thermal and mechanical properties and easy processing (ie, low viscosity) to enable Used as an electrical connector. However, contrary to conventional thinking, the polymer composition has been found to have excellent thermal and mechanical properties and processability.

For example, the melting temperature of the polymer composition can be, for example, about 180°C or greater, in some embodiments about 200°C, in some embodiments, about 210°C to about 400°C, and in some embodiments In about 220°C to about 380°C. Even at such melting temperatures, the ratio of the deflection temperature under load ("DTUL") (a measure of short-term heat resistance) to the melting temperature can still be kept relatively high. For example, the ratio can range from about 0.5 to about 1.00, in some embodiments from about 0.6 to about 0.95, and in some embodiments from about 0.65 to about 0.85. The specific DTUL value may, for example, be about 200°C or greater, in some embodiments about 200°C to about 350°C, such as about 210°C to about 320°C, such as about 230°C to about 290°C.

The polymer composition can also possess excellent mechanical properties, which can be useful when forming molded parts. For example, the polymer composition may exhibit about 20 MPa or more, in some embodiments about 30 MPa or more, in some embodiments about 40 MPa to about 300 MPa, and in some embodiments about 50 MPa. MPa to about 100 MPa tensile strength. The tensile properties can be measured at a temperature of 23°C according to ISO Test No. 527:2012. In addition, the polymer composition may exhibit about 20 MPa or more, in some embodiments about 50 MPa or more, in some embodiments about 60 MPa to about 300 MPa, and in some embodiments about 80 MPa to about Flexural strength of about 250 MPa. The flexural properties can be measured according to 178:2010 at a temperature of 23°C. In addition, the polymer composition can also possess high impact strength, which can be useful when forming a thinner substrate. The polymer composition may, for example, possess about 3 kJ/m ² or greater, in some embodiments about 5 kJ/m ² or greater, in some embodiments about 7 kJ/m ² or greater, Charpy notched impact strength of about 8 kJ/m ² to about 40 kJ/m ² in some embodiments, and about 10 kJ/m ² to about 25 kJ/m ^{2 in some embodiments.} The impact strength can be determined according to ISO test No. ISO 179-1:2010 at a temperature of 23°C.

Various embodiments of the present invention will now be described in more detail. I. Polymer composition A. Polymer matrix

Any one of a variety of polymers or a combination of polymers can generally be used in the polymer matrix. For example, the polymer can be semi-crystalline or crystalline in nature. In one embodiment, the polymer may be semi-crystalline. In another embodiment, the polymer may be crystalline. Additionally, in one embodiment, the polymer may be an aromatic polymer. Alternatively, in another embodiment, the polymer may be an aliphatic polymer.

Suitable polymers may include thermoplastic polymers. For example, these polymers may include, for example, polyolefins (e.g., ethylene polymers, propylene polymers, etc.), polyamides (e.g., aliphatic, semi-aromatic or aromatic polyamides), polyesters (For example, polyethylene terephthalate, polybutylene terephthalate, liquid crystal polymer), polyarylene sulfide, polyetherimide, polyacetal (for example, polyoxymethylene), polyphenylene ether (polyphenylene oxides), polyaryl ketones (for example, polyether ether ketone, polyether ketone ketone, etc.), polycarbonate, etc., and blends thereof.

Regardless, polymers can generally be regarded as "high performance" polymers, which have a relatively high glass transition temperature and/or high melting temperature. Such high-performance polymers can thereby provide a considerable degree of heat resistance to the polymer composition. For example, the polymer may have a temperature of about 30°C or higher, in some embodiments about 40°C or higher, in some embodiments about 50°C to about 250°C, and in some embodiments about 60°C to about 150°C glass transition temperature. The polymer may also have a temperature of about 180°C or higher, in some embodiments about 200°C or higher, in some embodiments about 210°C to about 400°C, and in some embodiments about 220°C to about 380°C Melting temperature. It is well known in this technology to use differential scanning calorimetry ("DSC") to determine the glass transition and melting temperature, such as by ISO test No. 11357-2:2013 (glass transition) and No. 11357-3:2011 No. (melt) to determine.

For example, one example of a suitable semi-crystalline aromatic polymer is an aromatic polyester, which is a condensation product of an aromatic dicarboxylic acid having 8 to 14 carbon atoms and at least one diol. Suitable diols may include, for example, neopentyl glycol, cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, and aliphatic diols of the _{formula HO(CH 2} ) _{n OH, where n} It is an integer from 2 to 10. Suitable aromatic dicarboxylic acids may include, for example, isophthalic acid, terephthalic acid, 1,2-bis(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether, etc., and combinations thereof . The fused ring may also exist in a form such as 1,4-naphthalene-dicarboxylic acid or 1,5-naphthalene-dicarboxylic acid or 2,6-naphthalene-dicarboxylic acid. Specific examples of such aromatic polyesters may include, for example, poly(ethylene terephthalate) (PET), poly(1,4-butylene terephthalate) (PBT), poly(1, 3-propylene terephthalate) (PPT), poly(1,4-butylene 2,6-naphthalate) (PBN), poly(ethylene 2,6-naphthalate) (PEN ), poly(1,4-cyclohexylene dimethylene terephthalate) (PCT) and copolymers and mixtures of the foregoing.

In a particular embodiment, the polymer may include polybutylene terephthalate. Polybutylene terephthalate may have a crystallinity of about 38% or higher, in some embodiments about 40% or higher, and in some embodiments about 45% or higher. The crystallinity of the polybutylene terephthalate polymer may generally be about 70% or less, in some embodiments about 65% or less, and in some embodiments about 60% or less. Differential scanning calorimetry (DSC) can be used to determine the percent crystallinity. Pyris 6 DSC from PerkinElmer Instruments can be used to perform this type of analysis. The detailed description of the calculation is obtained from Sichina, W. J. "DSC as problem solving tool: measurement of percent crystallinity of thermoplastics." Thermal Analysis Application Note (2000).

In addition, modified polyethylene terephthalate polymers and/or modified polybutylene terephthalate polymers or polyethylene terephthalate polymers and/or polyethylene terephthalate polymers can also be used. Copolymer of butylene formate polymer. For example, in one embodiment, a modified acid or a modified diol can be used to produce a modified polyethylene terephthalate polymer and/or a modified polybutylene terephthalate polymer. As used herein, the terms "modified acid" and "modified diol" define parts of the acid and diol repeating units that can form polyesters, respectively, and can modify the polyester to reduce its crystallinity or make the polyester amorphous. Compound. Of course, the polyester can be unmodified and does not contain a modified acid or modified diol. In any case, examples of modified acid components may include (but are not limited to) isophthalic acid, phthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, 1,12-dodecanedioic acid, etc. In fact, it is generally preferable to use its functional acid derivatives, such as dimethyl ester, diethyl ester or dipropyl ester of dicarboxylic acid. In practice, these acid anhydrides or acid halides can also be used. Examples of modified glycol components may include, but are not limited to, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3- Propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3- Cyclohexane dimethanol, 2,2,4,4-tetramethyl 1,3-cyclobutanediol, Z,8-bis(hydroxymethyl tricyclo-[5.2.1.0]-decane, where Z Represents 3, 4 or 5; 1,4-bis(2-hydroxyethoxy)benzene, 4,4′-bis(2-hydroxyethoxy)diphenyl ether [bishydroxyethyl bisphenol A], 4,4′-bis(2-hydroxyethoxy)diphenyl sulfide [bis-hydroxyethyl bisphenol S] and glycols containing one or more oxygen atoms in the chain, such as diethylene glycol, triethyl Glycols, dipropylene glycol, tripropylene glycol, etc. Generally speaking, these diols contain 2 to 18 carbon atoms, and in some embodiments 2 to 8 carbon atoms. Cycloaliphatic diols can be cis or trans Type configuration or a mixture of the two forms is used.

In some examples, the at least one polyester or copolyester present in the polymer composition may have an inherent viscosity (IV) of about 0.5 to about 0.9 dL/g, such as about 0.5 to about 0.8 dL/g. In one embodiment, for example, the inherent viscosity of polyester is about 0.65 to about 0.8 dL/g.

Polyarylene sulfide is also a suitable semi-crystalline aromatic polymer. The polyarylene sulfide used in the composition generally has a repeating unit of the following formula: -[(Ar ¹ ) _n -X] _m -[(Ar ² ) _i -Y] _j -[(Ar ³ ) _k -Z] _l -[(Ar ⁴ ) _o -W] _p -where Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are} independently 6 to 18 carbon atoms aryl extension units; W, X, Y and Z are independently It is a divalent linking group selected from the following: -SO ₂ -, -S-, -SO-, -CO-, -O-, -C(O)O- or alkylene groups of 1 to 6 carbon atoms Or an alkylene group, wherein at least one of the linking groups is -S-; and n, m, i, j, k, l, o, and p are independently 0, 1, 2, 3, or 4, with restrictions The condition is that the sum is not less than 2.

The aryl extension units Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may be optionally substituted or unsubstituted. Favorable arylene units are phenylene, biphenylene, naphthylene, anthracene and phenanthrene. Polyarylene sulfide generally includes greater than about 30 mol%, greater than about 50 mol%, or greater than about 70 mol% of arylene sulfide (-S-) units. For example, polyarylene sulfide may include at least 85 mol% of sulfur bonds directly connected to two aromatic rings. In a specific embodiment, the polyarylene sulfide is polyphenylene sulfide, which is defined herein as containing a phenylene sulfide structure -(C ₆ H ₄ -S) _n- (where n is 1 or greater Integer) as its component.

Synthetic techniques that can be used to prepare polyarylene sulfide are generally known in the art. For example, a process for preparing polyarylene sulfide may include reacting a sulfide ion-providing material (for example, an alkali metal sulfide) with a dihalogenated aromatic compound in an organic amide solvent. The alkali metal sulfide may be, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, or a mixture thereof. When the alkali metal sulfide is a hydrate or an aqueous mixture, the alkali metal sulfide may be treated according to a dehydration operation before the polymerization reaction. Alkali metal sulfides can also be generated in situ. In addition, a small amount of alkali metal hydroxide may be included in the reactant to remove impurities or to react the impurities (for example, to change these impurities into harmless substances), such impurities may exist in a very small amount with the alkali metal sulfide. Alkali metal polysulfide or alkali metal thiosulfate.

The dihalogenated aromatic compound can be (but not limited to): o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene , Dihalogenated biphenyl, dihalogenated benzoic acid, dihalogenated diphenyl ether, dihalogenated diphenyl sulfide, dihalogenated diphenyl sulfide or dihalogenated benzophenone. The dihalogenated aromatic compound may be used alone or in any combination thereof. Specific exemplary dihalogenated aromatic compounds may include, but are not limited to, p-dichlorobenzene; m-dichlorobenzene; o-dichlorobenzene; 2,5-dichlorotoluene; 1,4-dibromobenzene; 1,4 -Dichloronaphthalene; 1-methoxy-2,5-dichlorobenzene; 4,4'-dichlorobiphenyl; 3,5-dichlorobenzoic acid; 4,4'-dichlorodiphenyl ether; 4 ,4'-Dichlorodiphenyl Sulfide; 4,4'-Dichlorodiphenyl Sulfide and 4,4'-Dichlorobenzophenone. The halogen atom may be fluorine, chlorine, bromine or iodine, and two halogen atoms in the same dihalogenated aromatic compound may be the same or different from each other. In one embodiment, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, or a mixture of two or more compounds thereof is used as the dihalogenated aromatic compound. As known in the art, it is also possible to use monohalogenated compounds (not necessarily aromatics) in combination with dihalogenated aromatic compounds to form end groups of polyarylene sulfide or to adjust polymerization and/or poly The molecular weight of the arylene sulfide.

及具有下式結構之區段的聚芳硫醚共聚物：

或具有下式結構之區段的聚芳硫醚共聚物：

。The polyarylene sulfide can be a homopolymer or a copolymer. For example, the selective combination of dihalogenated aromatic compounds can produce polyarylene sulfide copolymers containing no less than two different units. For example, when p-dichlorobenzene is used in combination with m-dichlorobenzene or 4,4'-dichlorodiphenyl sulfide, a polyarylene sulfide copolymer containing segments with the following structure can be formed:

And polyarylene sulfide copolymers with segments of the following formula:

Or polyarylene sulfide copolymers with segments of the following formula:

.

The polyarylene sulfide can be linear, semi-linear, branched, or crosslinked. Linear polyarylene sulfide usually contains 80 mol% or more of the repeating unit -(Ar-S)-. Such linear polymers may also include a small amount of branched chain units or crosslinked units, but the amount of branched chain units or crosslinked units is usually less than about 1 mol% of the total monomer units of the polyarylene sulfide. The linear polyarylene sulfide polymer may be a random copolymer or a block copolymer containing the above-mentioned repeating unit. The semi-linear polyarylene sulfide may also have a small amount of crosslinked structure or branched chain structure of one or more monomers having three or more reactive functional groups introduced into the polymer. For example, the monomer component used to form the semi-linear polyarylene sulfide may include a certain amount of a polyhalogenated aromatic compound having two or more halogen substituents per molecule, which can be used to prepare branched chains. polymer. Such monomers can be represented by the formula R'X _n , where each X is selected from chlorine, bromine and iodine; n is an integer from 3 to 6; and R'is an n-valent one that may have up to about 4 methyl substituents In a polyvalent aromatic group, the total number of carbon atoms in R'is in the range of 6 to about 16. Examples of some polyhalogenated aromatic compounds with more than two halogen substitutions per molecule that can be used to form semi-linear polyarylene sulfides include: 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene , 1,3-Dichloro-5-bromobenzene, 1,2,4-triiodobenzene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene, 1,3,5-trichloro-2, 4,6-Trimethylbenzene, 2,2',4,4'-tetrachlorobiphenyl, 2,2',5,5'-tetra-iodobiphenyl, 2,2',6,6'- Tetrabromo-3,3',5,5'-tetramethylbiphenyl, 1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene, etc. and mixtures thereof.

Another example of a suitable semi-crystalline polymer may be polyamide. For example, in one embodiment, the polyamide can be an aromatic polyamide. In this regard, the aromatic polyamide may have a relatively high melting temperature, such as about 200°C or higher, in some embodiments about 220°C or higher, and in some embodiments about 240°C to about 320°C , As determined using differential scanning calorimetry according to ISO Test No. 11357. The glass transition temperature of aromatic polyamides is also generally about 110°C to about 160°C. In another embodiment, the aromatic polyamide may be an aliphatic polyamide. In this regard, the aliphatic polyamide may also have a relatively high melting temperature, such as about 180°C or higher, in some embodiments about 200°C or higher, and in some embodiments about 210°C to about 320 °C, as determined using differential scanning calorimetry according to ISO Test No. 11357. The glass transition temperature of aliphatic polyamides is also generally about 30°C to about 170°C.

Aromatic polyamides usually contain repeating units bonded together via amine bonds (NH-CO) and are formed by polycondensation of dicarboxylic acids (e.g. aromatic dicarboxylic acids), diamines (e.g. aliphatic diamines), etc. synthesis. For example, aromatic polyamides may contain aromatic repeating units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2 ,7-Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxy-diacetic acid, 1,3-phenylenedioxy-diacetic acid, diphthalic acid, 4, 4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfonate-4,4'-dicarboxylic acid, 4,4'-diphthalic acid, etc., and combinations thereof. Terephthalic acid is particularly suitable. Of course, it should also be understood that other types of acid units, such as aliphatic dicarboxylic acid units, multifunctional carboxylic acid units, etc., can also be used.

Aliphatic polyamides also usually contain repeating units held together by amine bonds (NH-CO). These polyamides can be synthesized via various techniques. For example, polyamides can be formed by ring-opening polymerization, such as the ring-opening polymerization of caprolactam. These polyamides can also be synthesized through polycondensation of dicarboxylic acids (for example, aliphatic dicarboxylic acids), diamines, and the like. For example, aromatic polyamides may contain aliphatic repeating units derived from aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, undecane Diacid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, dimer acid, cis-cyclohexane-1 ,4-Dicarboxylic acid and/or trans-cyclohexane-1,4-dicarboxylic acid, cis-cyclohexane-1,3-dicarboxylic acid and/or trans-cyclohexane-1,3-dicarboxylic acid, etc. and Its combination. Adipic acid is particularly suitable.

Polyamides may also contain aliphatic repeating units derived from aliphatic diamines, which generally have 4 to 14 carbon atoms. Examples of such diamines include linear aliphatic alkanediamines such as 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1, 9-nonane diamine, 1,10-decane diamine, 1,11-undecane diamine, 1,12-dodecane diamine, etc.; branched chain aliphatic alkane diamine, such as 2-methyl-1 ,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6 -Hexane diamine, 2,4-dimethyl-1,6-hexamethylene diamine, 2-methyl-1,8-octane diamine, 5-methyl-1,9-nonane diamine, etc.; and combination. Repeating units derived from 1,9-nonanediamine and/or 2-methyl-1,8-octanediamine are particularly suitable. Of course, other diamine units, such as alicyclic diamine, aromatic diamine, etc., can also be used.

Particularly suitable aromatic polyamides may include poly(nonylparaxylamide) (PA9T), poly(nonylparaxylylenediamide/nonyldecanediamide) (PA9T/ 910), poly(nonylparaphthalamide/nonyldodecane diamide) (PA9T/912), poly(nonylparaphthalamide/11-aminoundecane Amide) (PA9T/11), poly(nonyl-p-xylylenedimethamide/12-aminododecylamide) (PA9T/12), poly(decyl-p-xylylenedimethamide/11 -Aminoundecylamide) (PA10T/11), poly(decylpara-xylylenedimethamide/12-aminododecylamide) (PA10T/12), poly(decylparaphenylene) Dimethanamide/decyldecane diamide) (PA10T/1010), poly(decylparaxylylenedimethamide/decyldodecane diamide) (PA10T/1012), poly( Decyl-p-xylylenedimethamide/butylene hexanediamide) (PA10T/46), poly(decyl-p-xylylenedimethamide/caprolactamide) (PA10T/6), poly( Decylpara-xylylenedimethamide/hexylhexyldiamide) (PA10T/66), poly(decylpara-xylylenedimethamide/dodecyldodecyldiamide) (PA12T/1212), poly(dodecyl-p-xylylenedimethamide/caprolactam) (PA12T/6), poly(dodecyl-p-xylylenedimethamide/hexyl Amide) (PA12T/66), polyphthalamide (PPA), etc. Particularly suitable aliphatic polyamides may include polyamide 4,6, polyamide 5,10, polyamide 6, polyamide 6,6, polyamide 6,9, polyamide 6,10, Polyamide 6,12, polyamide 11, polyamide 12, etc. Still other examples of suitable aromatic polyamides are described in Harder et al ., U.S. Patent No. 8,324,307.

Another suitable semi-crystalline aromatic polymer that can be used in the present invention is polyaryl ether ketone. Polyaryl ether ketone is a semi-crystalline with a relatively high melting temperature, such as from about 300°C to about 400°C, in some embodiments from about 310°C to about 390°C, and in some embodiments from about 330°C to about 380°C polymer. The glass transition temperature may also be about 110°C to about 200°C. Particularly suitable polyaryl ether ketones are those which mainly include a phenyl moiety and/or an ether moiety bonded to a ketone. Examples of such polymers include polyether ether ketone ("PEEK"), polyether ketone ("PEK"), polyether ketone ketone ("PEKK"), polyether ketone ether ketone ketone ("PEKEKK"), polyether Ether ketone ketone ("PEEKK"), polyether-diphenyl-ether-ether-diphenyl-ether-phenyl-ketone-phenyl, etc., and their blends and copolymers.

其中， 環B為經取代或未經取代之6員芳基(例如1,4-伸苯基或1,3-伸苯基)、稠合至經取代或未經取代之5或6員芳基的經取代或未經取代之6員芳基(例如2,6-萘)或連接至經取代或未經取代之5或6員芳基的經取代或未經取代之6員芳基(例如4,4-聯伸二苯)；且 Y₁ 及Y₂ 獨立地為O、C(O)、NH、C(O)HN或NHC(O)。In addition to the polymers mentioned above, crystalline polymers can also be used in the polymer composition. Particularly suitable is liquid crystal polymer, which has a high degree of crystallinity that enables it to effectively fill the small space of the mold. To the extent that liquid crystal polymers can have a rod-like structure in their molten state (for example, a thermotropic nematic state) and exhibit crystalline behavior, the liquid crystal polymers are generally classified as "thermotropic." These polymers can also be generally referred to as polyesters. The polymer has a relatively high melting temperature, such as from about 250°C to about 400°C, in some embodiments from about 280°C to about 390°C, and in some embodiments from about 300°C to about 380°C. Such polymers can be formed from one or more types of repeating units known in the art. The liquid crystal polymer may, for example, contain one or more aromatic ester repeating units, the content of which is usually about 60 mol% to about 99.9 mol% of the polymer, and in some embodiments, about 70 mol% to about 99.5 mol%, And in some embodiments, from about 80 mol% to about 99 mol%. The aromatic ester repeat unit can generally be represented by the following formula (I):

Wherein, ring B is a substituted or unsubstituted 6-membered aryl group (for example, 1,4-phenylene or 1,3-phenylene), fused to a substituted or unsubstituted 5- or 6-membered aryl group A substituted or unsubstituted 6-membered aryl group (e.g. 2,6-naphthalene) or a substituted or unsubstituted 6-membered aryl group attached to a substituted or unsubstituted 5- or 6-membered aryl group ( For example, 4,4-diphenylene); and Y ₁ and Y _{2 are} independently O, C(O), NH, C(O)HN or NHC(O).

Generally, _{at least one of Y 1} and Y ₂ is C(O). Examples of such aromatic ester repeating units may include, for example, aromatic dicarboxylic acid repeating units (Y ₁ and Y _{2 in} formula I are C(O)), aromatic hydroxycarboxylic acid repeating units (of formula I Y ₁ is O and Y ₂ is C(O)) and various combinations thereof.

For example, aromatic dicarboxylic acid repeating units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl Ether-4,4'-dicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, bis(4-carboxyphenyl) ether, bis(4- Carboxyphenyl) butane, bis(4-carboxyphenyl)ethane, bis(3-carboxyphenyl)ether, bis(3-carboxyphenyl)ethane, etc., as well as its alkyl, alkoxy, aromatic Groups and halogen substituents and combinations thereof. Particularly suitable aromatic dicarboxylic acids may include, for example, terephthalic acid ("TA"), isophthalic acid ("IA"), and 2,6-naphthalenedicarboxylic acid ("NDA"). When used, repeating units derived from aromatic dicarboxylic acids (eg, IA, TA, and/or NDA) generally each constitute about 1 mol% to about 40 mol% of the polymer, and in some embodiments about 2 mol% To about 30 mol%, and in some embodiments from about 5 mol% to about 25 mol%.

It is also possible to use aromatic hydroxycarboxylic acid repeating units derived from aromatic hydroxycarboxylic acids, such as 4-hydroxybenzoic acid; 4-hydroxy-4'-biphenylcarboxylic acid; 2-hydroxy-6 -Naphthoic acid; 2-hydroxy-5-naphthoic acid; 3-hydroxy-2-naphthoic acid; 2-hydroxy-3-naphthoic acid; 4'-hydroxyphenyl-4-benzoic acid; 3'-hydroxyphenyl- 4-benzoic acid; 4'-hydroxyphenyl-3-benzoic acid, etc., and its alkyl, alkoxy, aryl and halogen substituents and combinations thereof. Particularly suitable aromatic hydroxycarboxylic acids are 4-hydroxybenzoic acid ("HBA") and 6-hydroxy-2-naphthoic acid ("HNA"). When used, repeating units derived from hydroxycarboxylic acids (for example, HBA and/or HNA) generally constitute about 20 mol% or more of the polymer, in some embodiments about 25 mol% or more, and in some embodiments In an example, about 30 mol% or higher, in some embodiments about 40 mol% or higher, in some embodiments about 50 mol% or higher, in some embodiments about 55 mol% to 100 mol%, And in some embodiments, from about 60 mol% to about 95 mol%.

Other repeating units can also be used in the polymer. In certain embodiments, for example, repeating units derived from aromatic diols such as hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and Hydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (or 4,4'-biphenol), 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl , 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)ethane, etc. and its alkyl, alkoxy, aryl and halogen substituents and combinations thereof. Particularly suitable aromatic diols may include, for example, hydroquinone ("HQ") and 4,4'-biphenol ("BP"). When used, repeating units derived from aromatic diols (e.g., HQ and/or BP) generally constitute about 1 mol% to about 50 mol% of the polymer, and in some embodiments, about 1 to about 40 mol%, In some embodiments, from about 2 mol% to about 40 mol%, in some embodiments from about 5 mol% to about 35 mol%, and in some embodiments from about 5 mol% to about 25 mol%. It can also be used, such as those derived from aromatic amines (e.g., acetaminophen ("APAP")) and/or aromatic amines (e.g., 4-aminophenol ("AP"), 3-aminophenol, 1,4- These repeating units of phenylenediamine, 1,3-phenylenediamine, etc.). In use, repeating units derived from aromatic amines (for example, APAP) and/or aromatic amines (for example, AP) generally constitute about 0.1 mol% to about 20 mol% of the polymer, and in some embodiments about 0.5 mol% to about 15 mol% and in some embodiments from about 1 mol% to about 10 mol%. It should also be understood that various other monomer repeat units can be incorporated into the polymer. For example, in certain embodiments, the polymer may contain one or more derived from non-aromatic monomers (such as aliphatic or cycloaliphatic hydroxycarboxylic acids, dicarboxylic acids, glycols, amides, amines, etc.) The repeating unit. Of course, in other embodiments, the polymer may be "fully aromatic" because it lacks repeating units derived from non-aromatic (e.g., aliphatic or cycloaliphatic) monomers.

Although not necessary, the liquid crystal polymer contains a relatively high content of cycloalkane hydroxycarboxylic acid and cycloalkanedicarboxylic acid, such as naphthalene-2,6-dicarboxylic acid ("NDA"), 6-hydroxy-2 -For repeating units of naphthoic acid ("HNA") or a combination thereof, the liquid crystal polymer can be a "high cycloalkane" polymer. That is, the total amount of repeating units derived from naphthenic hydroxycarboxylic acids and/or dicarboxylic acids (for example, NDA, HNA, or a combination of HNA and NDA) can be about 10 mol% or more of the polymer. About 12 mol% or higher in embodiments, about 15 mol% or higher in some embodiments, about 18 mol% or higher in some embodiments, and about 30 mol% or higher in some embodiments, In some embodiments about 40 mol% or higher, in some embodiments about 45 mol% or higher, in some embodiments 50 mol% or higher, in some embodiments about 55 mol% or higher , And in some embodiments from about 55 mol% to about 95 mol%. Without intending to be limited by theory, it is believed that such "homocycloalkane" polymers can reduce the tendency of the polymer composition to absorb water, which can help stabilize the dielectric constant and dissipation factor in the high frequency range. That is, according to ISO 62-1:2008, after being immersed in water for 24 hours, such high cycloalkane polymers generally have about 0.015% or less, in some embodiments about 0.01% or less, and in some The water absorption of about 0.0001% to about 0.008% in the examples. According to ISO 62-4:2008, after being exposed to a humid atmosphere (50% relative humidity) at a temperature of 23°C, the percycloalkane polymer may also have about 0.01% or less, and in some embodiments about 0.008% or more Small, and in some embodiments about 0.0001% to about 0.006% of hygroscopicity.

In one embodiment, for example, the repeating unit derived from HNA may constitute 30 mol% or more of the polymer, in some embodiments about 40 mol% or more, and in some embodiments about 45 mol% or more. Large, 50 mol% or greater in some embodiments, about 55 mol% or greater in some embodiments, and about 55 mol% to about 95 mol% in some embodiments. In such embodiments, the liquid crystal polymer may contain various other monomers, such as the content of about 1 mol% to about 50 mol%, and in some embodiments, about 1 mol% to about 20 mol%, and in some implementations In the example, about 2 mol% to about 10 mol% of aromatic hydroxycarboxylic acid (for example, HBA); the content is 1 mol% to about 40 mol%, and in some embodiments, about 5 mol% to about 25 mol% Aromatic dicarboxylic acid (for example, IA and/or TA); and/or aromatic diol with a content of about 1 mol% to about 40 mol%, and in some embodiments, about 5 mol% to about 25 mol% (For example, BP and/or HQ). In another embodiment, the repeating unit derived from NDA may constitute 10 mol% or higher of the polymer, in some embodiments about 12 mol% or higher, in some embodiments about 15 mol% or higher , And in some embodiments from about 18 mol% to about 95 mol%. In such embodiments, the liquid crystal polymer may also contain various other monomers, such as aromatic hydroxyl groups in an amount of about 20 mol% to about 60 mol%, and in some embodiments, about 30 mol% to about 50 mol%. Carboxylic acid (for example, HBA); content is about 2 mol% to about 30 mol%, and in some embodiments about 5 mol% to about 25 mol% aromatic dicarboxylic acid (for example, IA and/or TA) ; And/or the content is about 2 mol% to about 40 mol%, and in some embodiments, about 5 mol% to about 35 mol% of aromatic diols (for example, BP and/or HQ).

In addition, although it is not necessary, the liquid crystal polymer contains a minimum content of cycloalkane hydroxy carboxylic acid and cycloalkane dicarboxylic acid, such as naphthalene-2,6-dicarboxylic acid ("NDA"), 6-hydroxy-2 -A repeating unit of naphthoic acid ("HNA") or a combination thereof. The liquid crystal polymer can be a "lower cycloalkane" polymer. That is, the total amount of repeating units derived from naphthenic hydroxycarboxylic acids and/or dicarboxylic acids (for example, NDA, HNA or a combination of HNA and NDA) is usually no more than 10 mol% of the polymer. In some embodiments No more than about 15 mol% in some embodiments, no more than about 8 mol% in some embodiments, no more than about 6 mol% in some embodiments, and in some embodiments 1 mol% to about 5 mol% (e.g., 0 mol% %). In a specific embodiment, the liquid crystal polymer may be derived from 4-hydroxybenzoic acid ("HBA") and terephthalic acid ("TA") and/or isophthalic acid ("IA") and various other as appropriate Repetitive units of selected ingredients are formed. The repeating unit derived from 4-hydroxybenzoic acid ("HBA") can constitute about 10 mol% to about 80 mol% of the polymer, in some embodiments about 30 mol% to about 75 mol%, and in some embodiments In about 45 mol% to about 70 mol%. Repeating units derived from terephthalic acid ("TA") and/or isophthalic acid ("IA") can similarly constitute about 5 mol% to about 40 mol% of the polymer, in some embodiments about 10%. mol% to about 35 mol%, and in some embodiments from about 15 mol% to about 35%. It can also be used in an amount of about 1 mol% to about 30 mol%, in some embodiments, about 2 mol% to about 25 mol%, and in some embodiments, about 5 mol% to about 20%, derived from 4 , 4'-Biphenol ("BP") and/or hydroquinone ("HQ") repeating unit. Other possible repeating units may include those derived from 6-hydroxy-2-naphthoic acid ("HNA"), 2,6-naphthalenedicarboxylic acid ("NDA") and/or acetaminophen ("APAP") Repeating unit. In certain embodiments, such as when used, the repeating units derived from HNA, NDA, and/or APAP may each constitute about 1 mol% to about 35 mol%, and in some embodiments, about 2 mol% to about 30 mol%. %, and in some embodiments from about 3 mol% to about 25 mol%.

In certain embodiments, all liquid crystal polymers used in the polymer composition are "homocycloalkane" polymers such as those described above. However, in other embodiments, the "lower cycloalkane" liquid crystal polymer can also be used in the composition, where it is derived from cycloalkane hydroxycarboxylic acid and/or dicarboxylic acid (for example, NDA, HNA or a combination of HNA and NDA) The total amount of repeating units of the polymer is less than 10 mol%, in some embodiments about 8 mol% or less, in some embodiments about 6 mol% or less, and in some embodiments about 1 mol % To about 5 mol%. When employed, it is generally required that such lower cycloalkane polymers are only present in relatively low amounts. For example, when used, the lower cycloalkane liquid crystal polymer usually constitutes about 1 wt% to about 50 wt% of the total liquid crystal polymer in the composition, and in some embodiments, about 2 wt% to about 40 wt% , And in some embodiments about 5 wt% to about 30 wt%, and constitute about 0.5 wt% to about 45 wt% of the entire composition, in some embodiments about 2 wt% to about 35 wt%, and In some embodiments, from about 5 wt% to about 25 wt%. On the contrary, the homocycloalkane liquid crystal polymer usually constitutes about 50 wt% to about 99 wt% of the total amount of liquid crystal polymer in the composition, and in some embodiments, about 60 wt% to about 98 wt%, and in some embodiments In an example, it is about 70 wt% to about 95 wt%, and constitutes about 55 wt% to about 99.5 wt% of the entire composition, in some embodiments about 65 wt% to about 98 wt%, and in some embodiments about 75 wt% to about 95 wt%.

In some embodiments, it may be necessary to use a blend of polymers in a polymer matrix. For example, the polymer matrix may contain a first polymer that has a faster crystallization rate than the second polymer. In one embodiment, the first polymer may include polyethylene terephthalate and the second polymer may include polybutylene terephthalate polymer. Combining polymers with different crystallization rates can provide different advantages and benefits. For example, polymers with slower crystallization (e.g., polybutylene terephthalate) may tend to transfer to the surface of the part and provide good surface gloss and aesthetics, while polymers with faster crystallization (e.g., Polyethylene terephthalate) can enhance mechanical properties. When using this blend, it is generally required that the first polymer be present in an amount greater than the second polymer. For example, the weight ratio of the first polymer to the second polymer can be from about 1 to about 20, in some embodiments from about 2 to about 15, and in some embodiments from about 3 to about 10. The first polymer may, for example, constitute about 10 wt% to about 40 wt% of the polymer composition, in some embodiments about 15 wt% to about 35 wt%, and in some embodiments about 20 wt% to about About 30 wt%, and the second polymer may constitute about 1 wt% to about 10 wt% of the polymer composition, in some embodiments about 2 wt% to about 9 wt%, and in some embodiments about 3 wt% to about 8 wt%.

The polymer in the polymer matrix can be about 30 wt% or more of the polymer composition, in some embodiments about 40 wt% or more, in some embodiments about 40 wt% to about 99.5 wt%, It is present in an amount of about 50 wt% to about 95 wt% in some embodiments, in some embodiments about 60 wt% to about 90 wt%, and in some embodiments, about 60 wt% to about 85 wt%. B. Hollow inorganic filler

To help achieve the desired dielectric properties, the polymer composition may include hollow inorganic fillers. For example, at 100 MHz, these fillers may have about 3.0 or less, in some embodiments about 2.5 or less, in some embodiments about 1.1 to about 2.3, and in some embodiments about 1.2 To a dielectric constant of about 2.0. In addition, the hollow inorganic filler may have a specific size and contribute to the strength of the polymer composition, and may also enable the polymer composition to have a reduced weight and/or density due to the hollow nature.

Generally speaking, the hollow inorganic filler has a hollow space or cavity inside and can be synthesized using techniques known in the art. The hollow inorganic filler can be made of conventional materials. For example, the hollow inorganic filler may include alumina, silica, zirconia, magnesia, glass, fly ash, borate, phosphate, ceramic, and the like. In one embodiment, the hollow inorganic filler may include hollow glass fillers, hollow ceramic fillers, and mixtures thereof. In one embodiment, the hollow inorganic filler includes a hollow glass filler.

The insulating glass filler can be made of: soda lime borosilicate glass, soda lime glass, borosilicate glass, sodium borosilicate glass, sodium silicate glass or aluminosilicate glass. In this regard, in one embodiment, the composition of the glass (when not limited) may be at least about 65% by weight of SiO ₂ , 3 to 15% by weight of Na ₂ O, 8 to 15% by weight of CaO, 0.1 to 5% by weight of MgO, 0.01 to 3% by weight of Al ₂ O ₃ , 0.01 to 1% by weight of K ₂ O and other oxides (for example, Li ₂ O, Fe ₂ O ₃ , TiO ₂ , B ₂ O ₃ ). In another embodiment, the composition may be about 50 to 58% by weight of SiO ₂ , 25 to 30% by weight of Al ₂ O ₃ , 6 to 10% by weight of CaO, 1 to 4% by weight of Na ₂ O/ K ₂ O and 1 to 5 wt% of other oxides. In addition, in one embodiment, the hollow glass filler may include more alkaline earth metal oxides than alkali metal oxides. For example, the weight ratio of alkaline earth metal oxide to alkali metal oxide may be greater than 1, in some embodiments about 1.1 or greater, in some embodiments about 1.2 to about 4, and in some embodiments about 1.5 To about 3. Regardless of the above, it should be understood that the glass composition may vary depending on the type of glass used and still provide the benefits required by the present invention.

The hollow inorganic filler may have an average value of about 1 micrometer or greater, in some embodiments about 5 micrometers or greater, in some embodiments about 8 micrometers or greater, and in some embodiments about 1 micron to about 150 Micrometers, at least one size from about 10 microns to about 150 microns in some embodiments, and from about 12 microns to about 50 microns in some embodiments. In one embodiment, this average may refer to the d ₅₀ value.

In addition, the hollow inorganic filler may have about 3 microns or more, in some embodiments about 4 microns or more, in some embodiments about 5 microns to about 20 microns, and in some embodiments about 6 microns to about _{D 10 of} 15 microns. The hollow inorganic filler may have about 10 microns or more, in some embodiments about 15 microns or more, in some embodiments about 20 microns to about 150 microns, and in some embodiments about 22 microns to about 50 microns The D ₉₀ .

In this regard, the hollow inorganic filler may exist in the form of a size distribution, and the size distribution may be Gaussian, normal or non-normal. In one embodiment, the hollow inorganic filler may have a Gaussian size distribution. In another embodiment, the hollow inorganic filler may have a normal size distribution. In another embodiment, the hollow inorganic filler may have a non-normal size distribution. Examples of non-normal size distributions may include unimodal and multimodal (e.g., bimodal) size distributions.

When referring to the above size, such size can be any size. However, in one embodiment, such dimensions refer to diameters. For example, such values of size refer to the average diameter of the sphere. Dimensions such as average diameter can be measured according to 3M QCM 193.0. In this regard, in one embodiment, the hollow inorganic filler may refer to a hollow sphere, such as a hollow glass sphere. For example, the hollow inorganic filler may have an average aspect ratio of approximately 1. In general, the average aspect ratio may be about 0.8 or greater, in some embodiments about 0.85 or greater, in some embodiments about 0.9 to about 1.3, and in some embodiments about 0.95 to about 1.05.

In addition, the hollow inorganic filler may have relatively thin walls to help the dielectric properties of the polymer composition and reduce weight. The thickness of the wall may be about 50% or less of the average size (such as an average diameter) of the hollow inorganic filler, in some embodiments about 40% or less, in some embodiments about 1% to about 30%, and In some embodiments, from about 2% to about 25%.

In addition, the hollow inorganic filler may have a certain true density, which may allow easy handling and provide a polymer composition with reduced weight. Generally speaking, the true density refers to the quotient obtained by dividing the mass of the sample of the hollow filler by the true volume of that mass of the hollow filler, where the true volume is called the aggregated total volume of the hollow filler. In this regard, the actual density of the hollow inorganic filler may be about 0.1 g/cm ³ or more, in some embodiments about 0.2 g/cm ³ or more, and in some embodiments about 0.3 g/cm ³ or more. As large as about 1.2 g/cm ³ , and in some embodiments, from about 0.4 g/cm ³ or more to about 0.9 g/cm ³ . The true density can be determined according to 3M QCM 14.24.1.

Even if the filler is hollow, it can still have mechanical strength that allows the structural integrity of the filler to be maintained, so as to reduce the possibility of the filler being damaged during processing and/or use. In this regard, the isotactic pressure resistance of the hollow inorganic filler (that is, at least 80 vol%, such as at least 90 vol% of which the hollow filler can withstand) may be about 20 MPa or more, in some embodiments about 100 MPa Or greater, in some embodiments from about 150 MPa to about 500 MPa, and in some embodiments from about 200 MPa to about 350 MPa. Isotactic pressure can be measured according to 3M QCM 14.1.8.

The alkalinity of the hollow inorganic filler may be about 1.0 meq/g or less, in some embodiments about 0.9 meq/g or less, in some embodiments about 0.1 meq/g to about 0.8 meq/g, and In some embodiments, from about 0.2 meq/g to about 0.7 meq/g. Alkalinity can be measured according to 3M QCM 55.19. In order to provide a relatively low alkalinity, the hollow inorganic filler can be treated with a suitable acid (such as phosphoric acid).

In addition, the hollow inorganic filler may also include surface treatment to help provide better compatibility with the polymer and/or other components in the polymer composition. As an example, the surface treatment may be silylation. In particular, the surface treatment agent may include, but is not limited to, aminosilane, epoxysilane, and the like.

The hollow inorganic filler may, for example, constitute about 1 wt% or greater of the polymer composition, in some embodiments about 4 wt% or greater, in some embodiments about 5 wt% to about 40 wt%, and In some embodiments, from about 10 wt% to about 30 wt%. In addition, in order to provide beneficial properties, the weight ratio of the polymer to the hollow inorganic filler may be about 0.1 or greater, in some embodiments about 1 or greater, in some embodiments about 1.5 or greater, and in some embodiments In some embodiments, from about 0.1 to about 10, in some embodiments from about 1 to about 10, in some embodiments from about 2 to about 10, in some embodiments from about 2 to about 6, and in some embodiments from about 2 to about 5. C. Dielectric filler

In addition, the polymer composition can also use dielectric fillers to improve the properties of the polymer composition. For example, the dielectric filler can also be a filler capable of reducing the dielectric constant of the polymer composition. In addition, the dielectric filler can also help to improve other properties of the polymer composition. For example, dielectric fillers can also improve the thermal and mechanical properties of the polymer composition. These dielectric fillers can be dielectric inorganic fillers, dielectric organic fillers, or mixtures thereof. In one embodiment, the dielectric filler may be an inorganic dielectric filler. In another embodiment, the dielectric filler may be an organic dielectric filler. In another embodiment, the dielectric filler may be a mixture of an inorganic dielectric filler and an organic dielectric filler. In addition, in one embodiment, these dielectric fillers may be solid fillers so that they do not have internal cavities. These dielectric fillers may constitute about 1 wt% or greater of the polymer composition, in some embodiments about 2 wt% or greater, in some embodiments about 3 wt% to about 40 wt%, and In some embodiments, from about 5 wt% to about 25 wt%. In addition, since the hollow inorganic filler and the dielectric filler each have their own properties, the combination of these fillers in a specific ratio can provide beneficial properties to the polymer composition, such as the difference between dielectric, thermal and/or mechanical properties. Need to be balanced. In this regard, the weight ratio of the hollow inorganic filler to the dielectric filler may be about 0.1 or greater, in some embodiments about 0.1 to about 10, in some embodiments about 0.1 to about 5, and in some embodiments about 0.5 to about 4, and in some embodiments about 1 to about 2.

The specific properties of the dielectric filler can be changed as needed. For example, in one embodiment, the dielectric filler may be a fibrous filler. Fibrous fillers generally include fibers having a higher degree of tensile strength relative to their mass. For example, the ultimate tensile strength of the fiber (measured in accordance with ASTM D2101) is generally from about 1,000 to about 15,000 megapascals ("MPa"), in some embodiments from about 2,000 MPa to about 10,000 MPa, and in some embodiments Medium is about 3,000 MPa to about 6,000 MPa. To help maintain the required dielectric properties, such high-strength fibers can be made of materials that are generally insulating in nature, such as glass, ceramics, or minerals (e.g., alumina or silica), aromatic polyamides (e.g., made of Kevlar® sold by EI duPont de Nemours, Wilmington, Del.), minerals, polyolefins, polyesters, etc. In one embodiment, the fibrous filler may include glass fiber, mineral fiber, or a mixture thereof. For example, in one embodiment, the fibrous filler may include glass fibers. Particularly suitable glass fibers may include E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, and the like. In another embodiment, the fibrous filler may include mineral fibers. Mineral fibers may include silicates derived from silicate, such as island silicate, double island silicate, chain silicate (eg chain calcium silicate, such as wollastonite); chain silicate Calcium magnesium, such as tremolite; chain calcium magnesium iron silicate, such as actinolite; chain magnesium iron silicate, such as anthophyllite, etc.), phyllosilicate (such as phyllite) Acid aluminum, such as palygorskite), reticulated silicate, etc.; sulfate, such as calcium sulfate (such as dehydrated or anhydrous gypsum); mineral wool (such as mineral wool or slag wool), and the like. Especially suitable for chain silicates, such as wollastonite fibers available from Nyco Minerals under the trade name NYGLOS® (for example, NYGLOS® 4W or NYGLOS® 8).

In addition, although fibrous fillers can have many different sizes, fibers with a specific aspect ratio can help improve the mechanical properties of the polymer composition. That is, the aspect ratio (average length divided by the nominal diameter) is about 2 or greater, in some embodiments about 4 or greater, in some embodiments about 5 to about 50, and in some embodiments about Fibrous fillers ranging from 8 to about 40 can be especially beneficial. Such fibrous fillers may, for example, have about 10 microns or greater, in some embodiments about 25 microns or greater, in some embodiments about 50 microns or greater to about 800 microns or less, and In some embodiments, the weight average length is about 60 microns to about 500 microns. In addition, such fibrous fillers may, for example, have about 10 microns or greater, in some embodiments about 25 microns or greater, in some embodiments about 50 microns or greater to about 800 microns or less, And in some embodiments, the volume average length is about 60 microns to about 500 microns. The fibrous filler may also have about 5 microns or greater, in some embodiments about 6 microns or greater, in some embodiments about 8 microns to about 40 microns, and in some embodiments about 9 microns to about 20 microns. Nominal diameter in microns. The relative amount of fibrous filler can also be selectively controlled to help achieve the required mechanical and thermal properties without adversely affecting other properties of the polymer composition, such as its fluidity and dielectric properties. In this regard, at a frequency of 1 GHz, the fibrous filler may have about 6 or less, in some embodiments about 5.5 or less, in some embodiments about 1.1 to about 5, and in some embodiments about Dielectric constant of 2 to about 4.8.

The fibrous filler can be in a modified or unmodified form, for example, provided with a sizing agent or chemically treated to improve adhesion to plastics. In some examples, the glass fiber may be provided with a sizing agent to protect the glass fiber, make the fiber smooth, and also improve the adhesion between the fiber and the matrix material. If present, the sizing agent can include silane, film formers, lubricants, wetting agents, adhesives, optionally antistatic agents and plasticizers, emulsifiers and other additives as appropriate. In a particular embodiment, the sizing agent may include silane. Specific examples of silanes are aminosilanes, such as 3-trimethoxysilylpropylamine, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(3-trimethoxysilane Propyl)ethane-1,2-diamine, 3-(2-aminoethyl-amino)propyltrimethoxysilane, N-[3-(trimethoxysilyl)propyl]- 1,2-ethane-diamine.

If necessary, the dielectric filler may also include particulate filler. The polymer composition can also use particulate fillers as dielectric fillers to help achieve desired characteristics and/or colors. Particulate clay minerals can be particularly suitable for use in the present invention. Examples of such clay minerals include, for example, talc (Mg ₃ Si ₄ O ₁₀ (OH ₂ ), _{halloysite (Al 2} Si ₂ O ₅ (OH) ₄ ), kaolinite (Al ₂ Si ₂₎ O ₅ (OH) ₄ ), illite ((K,H ₃ O)(Al,Mg,Fe) ₂ (Si,Al) ₄ O ₁₀ [(OH) ₂ ,(H ₂ O)]) , Montmorillonite (Na,Ca) _0.33 (Al,Mg) ₂ Si ₄ O ₁₀ (OH) ₂ .nH ₂ O), vermiculite ((MgFe,Al) ₃ (Al,Si) ₄ O ₁₀ (OH) ₂ .4H ₂ O), palygorskite ((Mg,Al) ₂ Si ₄ O ₁₀ (OH).4(H ₂ O)), pyrophyllite ( Al ₂ Si ₄ O ₁₀ (OH) ₂ ), etc. and combinations thereof. As an alternative to clay minerals, or in addition to clay minerals, other particulate fillers can also be used. For example, other suitable particulate silicate fillers, such as mica, diatomaceous earth, etc., can also be used. For example, mica may be a mineral particularly suitable for use in the present invention. As used herein, the term "mica" is meant to generally include any of these species, such as muscovite (KAl ₂ (AlSi ₃ )O ₁₀ (OH) ₂ ), biotite (K(Mg,Fe) ₃ (AlSi ₃ )O ₁₀ (OH) ₂ ), Phlogopite (KMg ₃ (AlSi ₃ )O ₁₀ (OH) ₂ ), Lepidolite (K(Li,Al) _2-3 (AlSi ₃ )O ₁₀ (OH) ₂ ), sea green stone (K, Na) (Al, Mg, Fe) ₂ (Si, Al) ₄ O ₁₀ (OH) ₂ ), etc., and combinations thereof. Other types of mineral particulate fillers, such as silica, alumina, etc., can also be used.

The particulate filler may be in modified or unmodified form, for example, treated to improve properties. In some examples, the particulate filler can be fluorinated, for example as a coating. Fluorinated additives can be used to improve the processing of polymer compositions, such as by providing better mold filling, internal lubrication, mold release, etc. In certain embodiments, the fluorinated additives may include fluoropolymers containing hydrocarbon backbone polymers in which some or all of the hydrogen atoms are replaced by fluorine atoms. The backbone polymer may be a polyolefin and be formed from an unsaturated olefin monomer substituted with fluorine. The fluoropolymer may be a homopolymer of such a fluorine-substituted monomer or a copolymer of a fluorine-substituted monomer or a mixture of a fluorine-substituted monomer and a non-fluorine-substituted monomer. In addition to fluorine atoms, fluoropolymers can also be substituted with other halogen atoms, such as chlorine and bromine atoms. The representative monomers suitable for forming fluoropolymers used in the present invention are tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoroethyl vinyl ether, and perfluoromethyl vinyl ether. , Perfluoropropyl vinyl ether, etc. and their mixtures. Specific examples of suitable fluoropolymers include polytetrafluoroethylene, perfluoroalkyl vinyl ether, poly(tetrafluoroethylene-co-perfluoroalkyl vinyl ether), fluorinated ethylene-propylene copolymer, ethylene-tetrafluoroethylene Vinyl fluoride copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, etc. and their mixtures. The fluorinated additive may contain only the fluoropolymer, or it may also include other ingredients, such as those that help it be uniformly dispersed in the polymer composition. In one embodiment, for example, the fluorinated additive may include a combination of a fluoropolymer and a plurality of carrier particles. In such embodiments, for example, the fluoropolymer can be coated onto carrier particles, such as the particulate fillers mentioned above. D. Functional compound

If necessary, the polymer composition can also use functional compounds to additionally help reduce the melt viscosity of the polymer composition. For example, the functional compound may be a functional aromatic compound, a non-aromatic functional compound, or a mixture thereof. In one embodiment, for example, the polymer composition may include a non-aromatic functional compound. Such compounds can serve a variety of purposes, such as reducing melt viscosity. One such non-aromatic functional compound is water. If necessary, water can be added in the form of water produced under process conditions. For example, water can be added in the form of a hydrate that effectively "loses" water under process conditions (e.g., high temperature). Such hydrates include alumina trihydrate, copper sulfate pentahydrate, barium chloride dihydrate, calcium sulfate anhydride, etc., and combinations thereof. In a particular embodiment, the hydrate may include alumina trihydrate. When used, functional compounds (such as hydrates) can constitute about 0.001 wt% or greater of the polymer composition, in some embodiments about 0.005 wt% or greater, and in some embodiments about 0.005 wt% to about 2 wt%, and in some embodiments from about 0.01 wt% to about 1 wt%. E. Laser activatable additives

The polymer composition can be "laser-activatable" meaning that it contains additives that can be activated by the laser direct structuring ("LDS") process. In this process, the additives are exposed to the laser, which causes the release of metal. The laser draws a pattern of conductive elements on the part and leaves a rough surface with embedded metal particles. These particles serve as nuclei for crystal growth during subsequent plating processes (for example, copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, etc.).

Laser-activatable additives generally include spinel crystals, which can include two or more metal oxide cluster configurations within a definable crystal form. For example, the total crystal form may have the following general formula: AB ₂ O ₄ where A is a divalent metal cation, such as cadmium, chromium, manganese, nickel, zinc, copper, cobalt, iron, magnesium, tin, titanium, etc. and A combination thereof; and B is a trivalent metal cation, such as chromium, iron, aluminum, nickel, manganese, tin, etc., and combinations thereof.

Generally, A in the above formula provides the main cationic component of the first metal oxide cluster and B provides the main cationic component of the second metal oxide cluster. These oxide clusters can have the same or different structures. In one embodiment, for example, the first metal oxide cluster has a tetrahedral structure and the second metal oxide cluster has an octahedral cluster. In any case, the clusters can collectively provide an singularly identifiable crystal structure with enhanced sensitivity to electromagnetic radiation. Examples of suitable spinel crystals include, for example, MgAl ₂ O ₄ , ZnAl ₂ O ₄ , FeAl ₂ O ₄ , CuFe ₂ O ₄ , CuCr ₂ O ₄ , MnFe ₂ O ₄ , NiFe ₂ O ₄ , TiFe ₂ O ₄ , FeCr ₂ O ₄ , MgCr ₂ O ₄ and so on. Copper chromium oxide (CuCr ₂ O ₄ ) is particularly suitable for the present invention and is obtained from Shepherd Color Co. under the trade name "Shepherd Black 1GM".

The laser-activatable additive may constitute about 0.1 wt% to about 30 wt% of the polymer composition, in some embodiments about 0.5 wt% to about 20 wt%, and in some embodiments about 1 wt% to about 10 wt%. F. Other additives

The polymer composition may also include a variety of other additives, such as lubricants, thermally conductive fillers, pigments, antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-dripping additives, nucleating agents (for example, boron nitride ), flow regulators, coupling agents, antibacterial agents, pigments or other coloring agents, impact modifiers and other materials added to enhance properties and processability. Such optional materials can be used in the polymer composition in conventional amounts and according to conventional processing techniques. When used, for example, such additives generally constitute about 0.05 wt% to about 5 wt% of the polymer composition, and in some embodiments, about 0.1 wt% to about 1 wt%.

In one embodiment, the polymer composition may include a lubricant. For example, the lubricant may include polyolefin wax (for example, polyethylene wax), amide wax, fatty acid ester wax, and the like. In one embodiment, the lubricant may include polyolefin wax, such as polyethylene wax. The lubricant may also be fatty acid ester wax. Fatty acid ester waxes can be obtained, for example, by the following steps: oxidatively bleaching crude natural waxes and then esterifying fatty acids with alcohols. In some cases, the alcohol may have 1 to 4 hydroxyl groups and 2 to 20 carbon atoms. When the alcohol is polyfunctional (for example, 2 to 4 hydroxyl groups), a carbon number of 2 to 8 is particularly required. Particularly suitable polyfunctional alcohols may include diols (e.g., ethylene glycol, propylene glycol, butylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclic Hexanediol), trihydric alcohols (such as glycerol and trimethylolpropane), tetrahydric alcohols (such as neopentylerythritol and erythritol), and so on. Aromatic alcohols may also be suitable, such as o-tolyl methanol, m-tolyl methanol and p-tolyl methanol, chlorobenzyl alcohol, bromobenzyl alcohol, 2,4-dimethylbenzyl alcohol, 3,5-dimethyl Benzyl alcohol, 2,3,5-cumyl alcohol, 3,4,5-trimethylbenzyl alcohol, p-isopropyl benzyl alcohol, 1,2-phthalimidine alcohol, 1,3-bis (Hydroxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, pseudocumenyl glycol, mesitylene glycol, and mesitylene glycerol. Particularly suitable fatty acid esters for use in the present invention are derived from montanic waxes. For example, Licowax® OP (Clariant) contains montanic acid partially esterified with butanediol and montanic acid partially saponified with calcium hydroxide. Therefore, Licowax® OP contains a mixture of montanic acid ester and calcium montanate. Other montanic acid esters that can be used include Licowax® E, Licowax® OP and Licolub® WE 4 (all from Clariant), such as montanic acid esters obtained in the form of secondary products of oxidative refining of raw montan wax. Licowax® E and Licolub® WE 4 contain montanic acid esterified with ethylene glycol or glycerol.

In one embodiment, the polymer composition may include black pigments. Black pigments generally include multiple types of carbon black particles, such as furnace carbon black, channel carbon black, acetylene carbon black, lamp carbon black, and the like. The carbon black particles may have any desired shape, such as granular, flake (scale), and the like. The average size (e.g., diameter) of the particles can be, for example, between about 1 to about 200 nanometers, in some embodiments about 5 to about 150 nanometers, and in some embodiments about 10 to about 100 nanometers. range. It is also generally required that the carbon black particles are relatively pure, such as polynuclear aromatic hydrocarbons (e.g., benzoic hydrocarbons) with a content of about 1 parts per million ("ppm") or less, and in some embodiments, about 0.5 ppm or less. [a] Pyrene, naphthalene, etc.). For example, the black pigment may contain benzo[a]pyrene in an amount of about 10 parts per billion ("ppb") or less, and in some embodiments, about 5 ppb or less.

If necessary, the black pigment may include a carrier resin that can encapsulate carbon black particles, thereby providing various benefits. For example, the carrier resin can enhance the ability of the particles to be manipulated and incorporated into the base polymer composition. Although any known carrier resin can be used for this purpose, in certain embodiments, the carrier resin can be the same as the polymer used in the polymer matrix of the polymer composition. If necessary, the carrier resin can be pre-blended with carbon black particles to form a pigment master mixture that is later combined with the polymer. When employed, the carrier resin generally constitutes about 50 wt% to about 95 wt% of the master mix, in some embodiments about 60 wt% to about 90 wt%, and in some embodiments about 70 wt% to about 85 wt% %, and carbon black particles generally constitute about 5 wt% to about 50 wt% of the master mixture, in some embodiments about 10 wt% to about 40 wt%, and in some embodiments about 15 wt% to about 30 wt% %. Of course, other components can also be incorporated into the master mix. II. Formation

The components used to form the polymer composition can be combined together using any of a variety of different techniques known in this technology. In a specific embodiment, for example, the polymer (optionally hollow inorganic filler and/or dielectric filler) and other optional additives are melt-processed in an extruder to form a mixture to form a polymer composition. The mixture can be melt-kneaded in a single-screw or multi-screw extruder at a temperature of about 250°C to about 450°C. In one embodiment, the mixture may be melt processed in an extruder that includes multiple temperature zones. The temperature of the individual zone is usually set within about -60°C to about 25°C relative to the melting temperature of the polymer. For example, the mixture can be melt processed using a twin screw extruder, such as a Leistritz 18-mm co-rotating fully intermeshing twin screw extruder. The universal screw design can be used for melt processing of mixtures. In one embodiment, the mixture including all components can be fed into the feed port in the first cylinder by means of a positive displacement feeder. In another embodiment, as we know, different components can be added at different addition points in the extruder. For example, the polymer can be applied at the feed port, and certain additives (for example, hollow inorganic fillers, dielectric fillers, and/or other optional materials) can be supplied at the same or different temperature zones downstream of it. additive). In any case, the resulting mixture can be melted and mixed, and then extruded through a die. The extruded polymer composition can then be quenched in a water bath to solidify and pelletized in a pelletizer, followed by drying.

The melt viscosity of the polymer composition is generally low enough so that it can easily flow into the cavity of the mold to form a small circuit substrate. For example, in a particular embodiment, the polymer composition may have about 5 Pa-s or more, in some embodiments about 10 Pa-s or more, in some embodiments about 10 Pa-s To about 500 Pa-s, in some embodiments about 5 Pa-s to about 150 Pa-s, in some embodiments about 5 Pa-s to about 100 Pa-s, in some embodiments about 10 Pa-s s to about 100 Pa-s, in some embodiments about 15 to about 90 Pa-s, and in some embodiments about 20 Pa-s to about 60 Pa-s melt viscosity, such as higher than the polymer The melting temperature is measured at a temperature of 20°C at a shear rate of ^{1,000 sec-1.} The melt viscosity can be determined according to 11443:2005.

In addition, the polymer composition may have a relatively low density. For example, the density may be about 3 g/cm ³ or less, in some embodiments about 2.5 g/cm ³ or less, in some embodiments about 0.1 g/cm ³ to about 2 g/cm ³ , And in some embodiments about 0.5 g/cm ³ to about 1.6 g/cm ³ . The density can be determined according to ISO 1183.

In addition, the polymer composition may have a certain X value as described in U.S. Patent No. 6,495,616 incorporated herein by reference and defined by the following equation: X=100×[(100/ρ ₀ +α /ρ ₁ +β/ρ ₃ )−(100+α+β)/ρ)(α/ρ ₁ −α/ρ ₂ ) where α represents the amount of hollow inorganic filler (weight parts based on 100 parts by weight of polymer ), β represents the amount of dielectric (for example, fibrous) filler (in parts by weight based on 100 parts by weight of polymer), ρ ₀ represents the specific gravity of the polymer, ρ ₁ represents the true specific gravity of the hollow inorganic filler, and ρ ₂ represents the hollow The material specific gravity of the inorganic filler, ρ ₃ represents the specific gravity of the dielectric (for example, fibrous) filler, and ρ represents the specific gravity of ASTM No. 4 dumbbells (having a thickness of 2.5 mm) obtained by injection molding the polymer composition . In one embodiment, X may be 10-50. In another embodiment, X may be less than 10 or greater than 50. For example, in one embodiment, X may be less than 10. In another embodiment, X may be greater than 50. III. Molded parts

Once formed, the polymer composition can be molded into the desired shape for a specific application. Generally, the molded part is molded using a one-component injection molding process, in which dried and pre-heated plastic particles are injected into the mold. In one embodiment, the molded part or shape may be an electrical connector as mentioned above. Electrical connectors can find specific applications in 5G radio frequency systems.

Referring to FIG. 3, for example, an embodiment of the 5G communication system 300 may include a base station 302, one or more relay stations 304, one or more user computing devices 306, and one or more Wi-Fi repeaters 308 (For example, "ultra-micro cell") and/or other suitable antenna components used in the 5G communication system 300. The repeater 304 can be configured to facilitate the user computing device 306 and/or other relays by relaying or "repeating" signals between the base station 302 and the user computing device 306 and/or repeater 304 The station 304 communicates with the base station 302. The base station 302 may include a MIMO antenna array 310 configured to receive and/or transmit radio frequency signals 312 with the repeater 304, the Wi-Fi repeater 308, and/or directly with the user computing device 306 . The user computing device 306 is not necessarily limited by the present invention and includes devices such as 5G smart phones.

The MIMO antenna array 310 can employ beam steering to focus or direct the radio frequency signal 312 relative to the repeater station 304. For example, the MIMO antenna array 310 may be configured to adjust the elevation angle 314 relative to the X-Y plane and/or the heading angle 316 defined in the Z-Y plane and relative to the Z direction.

Similarly, one or more of the repeater 304, the user computing device 306, and the Wi-Fi repeater 308 can use beam steering to directionally tune the devices 304, 306, 308 relative to the MIMO of the base station 302 The sensitivity and/or power transmission of the antenna array 310 (for example, by adjusting one or both of the relative elevation angle and/or relative azimuth angle of each device) to improve the reception and/or transmission relative to the MIMO antenna array 310 ability.

The electrical connector can be used to communicatively couple different components of the base station 302, the relay station 304, and/or the user computing device 306. For example, the base station 302, the relay station 304, and/or the user computing device 306. Such antennas and/or antenna arrays can be communicatively coupled with one or more integrated circuits, processors, memories, etc. For example, the front-end module can be used to control the transmission and/or reception of radio frequency signals using antennas and/or antenna arrays. The electrical connector can be communicatively coupled to any of the above devices.

The invention can be better understood with reference to the following examples. testing method

Melt viscosity : According to ISO Test No. 11443:2005, the ^{melt viscosity can be measured at a shear rate of 1,000 s -1} and a temperature of 15°C higher than the melting temperature (for example, about 350°C) using a Dynisco LCR7001 capillary rheometer (Pa- s). The rheometer hole (mold) has a diameter of 1 mm, a length of 20 mm, an L/D ratio of 20.1, and an entrance angle of 180°. The diameter of the barrel is 9.55 mm + 0.005 mm, and the length of the rod is 233.4 mm.

Melting temperature : The melting temperature ("Tm") can be determined by differential scanning calorimetry ("DSC") known in this technology. The melting temperature is the differential scanning calorimetry (DSC) peak melting temperature as determined by ISO Test No. 11357-2:2013. Under the DSC program, the DSC measurement performed on the TA Q2000 instrument is used to heat the sample and cool the sample at 20°C per minute as stated in the ISO standard 10350.

Deflection temperature under load (" DTUL "): Deflection temperature under load can be determined according to ISO Test No. 75-2:2013 (technically equivalent to ASTM D648-07). More specifically, a test strip sample with a length of 80 mm, a thickness of 10 mm, and a width of 4 mm can be subjected to a three-point bending test along the edges, where the specified load (maximum external fiber stress) is 1.8 MPa. The sample can be lowered into a silicone oil bath, where the temperature is increased at 2°C per minute until it deflects by 0.25 mm (0.32 mm for ISO test No. 75-2:2013).

Tensile modulus, tensile stress and tensile elongation: The tensile properties can be tested according to ISO Test No. 527:2012 (technically equivalent to ASTM D638-14). Modulus and strength can be measured on the same test strip sample with a length of 80 mm, a thickness of 10 mm and a width of 4 mm. The test temperature can be about 23°C and the test speed can be 1 mm/min or 5 mm/min.

Flexural modulus, flexural stress and flexural elongation : The flexural characteristics can be tested according to ISO Test No. 178:2010 (technically equivalent to ASTM D790-10). This test can be performed on a 64 mm support span. It can be tested on the center part of the uncut ISO 3167 multi-purpose rod. The test temperature can be about 23°C and the test speed can be 2 mm/min.

Unnotched and notched Charpy impact strength : The Charpy impact strength can be tested according to ISO Test No. 179-1:2010 (technically equivalent to ASTM D256-10, Method B). The type 1 sample size (length of 80 mm, width of 10 mm and thickness of 4 mm) can be used for this test. When testing the impact strength of the notch, the notch can be a type A notch (0.25 mm base circle radius). A single-tooth milling machine can be used to cut samples from the center of a multi-purpose rod. The test temperature can be about 23°C.

Dielectric constant ( " Dk " ) and dissipation factor ( " Df " ) : use known split dielectric resonator technology, such as Baker-Jarvis, et al., IEEE Trans. on Dielectric and Electrical Insulation, 5(4) , page 571 (1998) and Krupka, et ^{al., Proc 7 th International Conference on Dielectric} Materials:. Measurements and Applications, IEEE Conference publication No. 430 (September 1996) the dielectric constant was measured as described (or Relative static permittivity) and dissipation factor. More specifically, a sheet sample with a size of 80 mm×80 mm×1 mm is inserted between two fixed dielectric resonators. The permittivity component in the plane of the resonator quantity test sample. Five (5) samples are tested and the average value is recorded. The split resonator can be used for dielectric measurement in low gigahertz areas such as 1 GHz, 2 GHz, or 10 GHz. Example 1

Samples 1 to 5 are formed of liquid crystal polymer (LCP 1 or LCP 2), hollow glass spheres, mica, wollastonite, glass powder and/or glass fiber. LCP 1 is formed by 43% HBA, 9% TA, 29% HQ and 20% NDA. LCP 2 is formed by 48% HNA, 2% HBA, 25% BP and 25% TA. The hollow glass spheres have an average diameter of 18 microns. The glass powder has a dielectric constant of 4.8, as measured at a frequency of 1 GHz. In addition, the glass fiber used has an initial length of 3 mm or 4 mm. The polymer composition may also include polyethylene lubricants, alumina trihydrate, pigments and/or various other trace additives. A 25-mm single screw extruder was used to perform the mixing. Table 1 sample 1 2 3 4 5 6 LCP 1 - - 77.3 67.3 67.3 - LCP 2 72.8 71.8 - - - 71.8 Hollow glass ball 17 17 20 15 15 17 Mica - - - 15 - - Wollastonite - - - - 15 - Glass powder - 1 - - 1 Fiberglass (4 mm length) - - - - - 10 Fiberglass (3 mm long) 10 10 - - - Alumina trihydrate 0.2 0.2 - - - 0.2 Polyethylene - - 0.2 0.2 0.2 - Black Pigment Master Mix - - 2 2 2 - Other additives - - 0.5 0.5 0.5 -

Then test the thermal and mechanical properties of the sample. The results are given in Table 2 below. Table 2 sample 1 2 3 4 5 6 Dielectric constant (10 GHz) 3.03 3.01 3.0 3.2 3.2 2.93 Dissipation factor (10 GHz) 0.002 0.002 0.003 0.003 0.003 0.003 Dielectric constant (2 GHz) - 2.99 - - - - Dissipation factor (2 GHz) - 0.002 - - - - DTUL under 1.8 MPa (℃) 289 291 243 243 250 - Tensile strength (MPa) 78 86 77 66 65 99 Flexural strength (MPa) 122 - - - - - Impact strength (kJ/m ² ) 11 7 15 6 6 - Density (g/cm ³ ) 1.22 1.18 1.14 1.27 1.28 - Example 2

Sample 7 contains 100 wt% LCP 3 for the connector. The LCP 3 is formed by 62% HNA, 2% HBA, 18% TA, and 18% BP. The samples were injection molded into thin sheets (60 mm × 60 mm) and tested for thermal and mechanical properties. The results are given below. Table 3 Sample 7 Dk at 10 GHz 3.36 Df at 10 GHz 0.0007 Tensile strength (MPa) 165 Tensile modulus (MPa) 15,382 Tensile elongation (%) 1.2 Flexural strength (MPa) 215 Flexural modulus (MPa) 15,792 Charpy gap (KJ/m ² ) 17.3 DTUL under 1.8 MPa (℃) 313.5 Melting temperature (℃) (The first heating of DSC) 334 Example 3

Samples 8 to 15 are formed by different combinations of liquid crystal polymer (LCP 2), ground and/or chopped glass fiber tow (aspect ratio = 4), mica (MICA 1 and MICA 2) and silicon dioxide . MICA 1 has an average particle size of 25 microns and MICA 2 has an average particle size of 60 microns. An 18 mm single screw extruder was used to perform the mixing. The parts are injection-molded samples of thin sheets (60 mm × 60 mm). Table 4 8 9 10 11 12 13 14 15 LCP 2 78 68 78 78 68 78 68 80 Ground glass fiber - 10 - - 10 - - - Flat glass fiber - - 10 15 - 10 10 - MICA 1 twenty two twenty two 12 17 - - - 20 MICA 2 twenty two 12 - - Silicon dioxide - - - - - - 12 -

Test the thermal and mechanical properties of samples 8-15. The results are given in the table below. Table 5 sample 8 9 10 11 12 13 14 15 Dielectric constant (2 GHz) 3.96 3.95 3.96 4.03 4.04 4.07 3.67 3.7 Dissipation factor (2 GHz) 0.0014 0.0015 0.0015 0.0021 0.0021 0.0019 0.0016 0.0009 Dielectric constant (10 GHz) - 4.03 - - - - - 3.78 Dissipation factor (10 GHz) - 0.0015 - - - - - 0.0078 DTUL under 1.8 MPa (℃) - - - - - - - 298 Charpy gap (kJ/m ² ) - - - - - - - 8.6 Charpy notch (kJ/m ² ) - - - - - - - - Tensile strength (MPa) 142 146 124 134 128 134 121 179 Tensile modulus (MPa) 13,731 14,422 13,385 13,851 13,578 14,691 10,186 12,795 Tensile elongation (%) 1.96 1.64 1.39 1.74 1.57 1.37 2.1 2.3 Flexural strength (MPa) 195 222 204 206 204 211 182 205 Flexural modulus (MPa) 13,349 14,074 13,307 13,492 13,331 14,361 10,283 12,888 Flexural elongation (%) 2.55 2.26 2.17 2.3 2.3 1.97 2.77 2.9 Melt viscosity under 1,000 s ^-1 (Pa-s) 38 48 44 39 36 52 56 25.8 Melting temperature (℃) (The first heating of DSC) 343 345 344 344 343 343 346 340 Example 4

Sample 16 is formed of liquid crystal polymer (LCP 2 and LCP 4), hollow glass spheres, glass powder, glass fiber, and alumina trihydrate. LCP 4 is formed by 60% HBA, 4% HNA, 18% TA and 18% BP. The glass powder has a dielectric constant of 4.8, as measured at a frequency of 1 GHz. A 25-mm single screw extruder was used to perform the mixing. Table 6 sample 16 LCP 2 49.8 LCP 4 15.4 Hollow glass ball 17.0 Glass powder 1.0 Fiberglass (4 mm length) 10.0 Alumina trihydrate 0.2 Copper chromite 6.6

Then test the thermal and mechanical properties of the sample. The results are given in Table 7 below. Table 7 sample 16 Dielectric constant (2 GHz) 3.07 Dissipation factor (2 GHz) 0.0043 Dielectric constant (10 GHz) 3.14 Dissipation factor (10 GHz) 0.0035 Melt viscosity under 1,000 s ^-1 (Pa-s) 55.5 Melt viscosity under 400 s ^-1 (Pa-s) 88.9 Melting temperature (℃) 338.6 DTUL under 1.8 MPa (℃) 217 Tensile strength (MPa) 81 Tensile modulus (MPa) 7,658 Tensile elongation (%) 1.41 Flexural strength (MPa) 116 Flexural modulus (MPa) 7,241 Flexural elongation (%) 1.91 Charpy notched impact strength (kJ/m ² ) 3.1 Charpy non-notched impact strength (kJ/m ² ) 7.3

These and other modifications and changes of the present invention can be practiced by ordinary skilled persons without departing from the spirit and scope of the present invention. In addition, it should be understood that the aspects of the various embodiments may be interchanged in whole or in part. In addition, those skilled in the art should understand that the previous description is only by way of example, and is not intended to limit the invention further described in the scope of such appended applications.

3: wire 5: Terminal 10: The first shell 10a: Assembly notch 20: second shell 22: terminal accommodating cavity 28: Locking part 100: electrical connector 200: electrical connector 224: Opposite Wall 225: Aisle/Space 300: 5G communication system 302: base station 304: Repeater 306: User Computing Device 308: Wi-Fi Repeater 310: MIMO antenna array 312: RF signal 314: Elevation 316: Azimuth C1: Wiring material side part C2: Board side part/board side connector P: Circuit board w: width

The complete and achievable disclosure content of the present invention, including its best mode for those familiar with the art, is described in more detail in the remainder of this specification, including with reference to the accompanying drawings, in which:

Figure 1A depicts a thin-walled electrical connector according to an aspect of the present invention;

Figure 1B depicts an enlarged view of a part of the thin-walled connector of Figure 1A;

Figure 2 is an exploded perspective view of another embodiment of a thin-walled connector and a connector socket that can be formed according to the present invention; and

Figure 3 depicts a 5G communication system including a base station, a repeater, a user computing device, and a Wi-Fi repeater.

100: electrical connector

Claims (30)

An electrical connector comprising at least two opposite walls defining a passage for accommodating connection pins, wherein the walls have a width of about 500 microns or less, and the walls are made of a polymer containing a polymer matrix A composition is formed, and the polymer matrix contains at least one polymer having a glass transition temperature of about 30° C. or greater and an amount of about 30 wt% or greater of the composition, wherein the polymer composition exhibits about 4 or more Small dielectric constant and dissipation factor of about 0.02 or less, as measured at a frequency of 10 GHz. The electrical connector of claim 1, wherein the polymer composition exhibits a dielectric constant of about 3.5 or less and a dissipation factor of about 0.005 or less, as measured at a frequency of 10 GHz. The electrical connector of claim 1 or 2, wherein the walls have a width of about 200 to about 400 microns. The electrical connector of claim 1 or 2, wherein the polymer comprises polyolefin, polyamide, polyester, polyarylene sulfide, polyaryl ketone, or a mixture thereof. The electrical connector of claim 1 or 2, wherein the polymer comprises polyester, and the polyester comprises liquid crystal polymer. The electrical connector of claim 5, wherein the liquid crystal polymer is an aromatic polyester containing repeating units derived from 4-hydroxybenzoic acid. The electrical connector of claim 5, wherein the liquid crystal polymer has a total amount of about 10 mol% or more of repeating units derived from cycloalkanehydroxycarboxylic acid and/or cycloalkanedicarboxylic acid. The electrical connector of claim 5, wherein the liquid crystal polymer has a total amount of about 10 mol% or more of repeating units derived from naphthalene-2,6-dicarboxylic acid. The electrical connector of claim 5, wherein the liquid crystal polymer contains a repeating unit derived from 6-hydroxy-2-naphthoic acid in an amount of about 30 mol% or more. The electrical connector of claim 5, wherein the liquid crystal polymer contains a repeating unit derived from 6-hydroxy-2-naphthoic acid in an amount of about 50 mol% or more. The electrical connector of claim 5, wherein the liquid crystal polymer is present in an amount of about 50 wt% to about 85 wt%. The electrical connector of claim 1 or 2, wherein the polymer composition further comprises at least one hollow inorganic filler having a dielectric constant of about 3.0 or less at a frequency of 100 MHz. The electrical connector of claim 1 or 2, wherein the polymer composition further comprises at least one dielectric filler, and the dielectric filler comprises a fibrous filler, a particulate filler or a mixture thereof. The electrical connector of claim 1 or 2, wherein the polymer composition further comprises at least one hollow inorganic filler and at least one dielectric filler having a dielectric constant of about 3.0 or less at a frequency of 100 MHz, wherein the at least The weight ratio of a hollow inorganic filler to the at least one dielectric filler is about 0.1 to about 10. The electrical connector of claim 14, wherein the weight ratio of the at least one polymer to the at least one hollow inorganic filler is about 0.1 to about 10. The electrical connector of claim 14, wherein the at least one hollow inorganic filler comprises hollow glass spheres. The electrical connector of claim 16, wherein the hollow glass balls have an aspect ratio of about 0.8 to about 1.2. The electrical connector of claim 16, wherein the hollow glass balls have an average diameter of about 1 micrometer to about 150 micrometers. Such as the electrical connector of claim 16, wherein the thickness of the wall of the hollow glass balls is about 40% or less of the average diameter of the hollow glass balls. The electrical connector of claim 14, wherein the at least one hollow inorganic filler is present in an amount of about 5 wt% to about 40 wt%. The electrical connector of claim 13, wherein the fibrous filler comprises glass fiber. Such as the electrical connector of claim 13, wherein the fibrous filler comprises wollastonite. The electrical connector of claim 13, wherein the particulate filler contains mica. The electrical connector of claim 13, wherein the at least one dielectric filler is present in an amount of about 3 wt% to about 40 wt%. The electrical connector of claim 1 or 2, wherein the polymer composition has a melt viscosity of about 10 to about 100 Pa-s, such as a ^{shear rate of 1,000 seconds-1} and higher than the melting of the at least one polymer The temperature is measured at a temperature of 20°C. The electrical connector of claim 1 or 2, wherein the polymer composition further comprises a laser-activatable additive. A 5G radio frequency communication system, which includes: A radio frequency component configured to operate at greater than about 3 GHz, the radio frequency component including connection pins; and An electrical connector coupled to the radio frequency component, the electrical connector comprising at least two opposite walls defining an aisle therebetween, wherein the connection pin of the radio frequency component is accommodated in the aisle of the electrical connector, wherein The walls have a width of about 500 microns or less, and the walls are formed of the polymer composition according to any one of claims 1 to 26. Such as the 5G radio frequency communication system of claim 27, wherein the radio frequency component is configured to operate at greater than 28 GHz. For example, the 5G radio frequency communication system of claim 27, wherein the radio frequency component includes at least one of a front-end module or an antenna. For example, the 5G radio frequency communication system of claim 27, wherein the radio frequency component is included in at least one of a base station, a user computing device, a repeater, a repeater, or a 5G smart phone.

Images